The present invention relates to novel fungicidal compositions for the treatment of phytopathogenic diseases of crop plants and against infestation on propagation stock of plants or on other vegetable material, especially phytopathogenic fungi, and to a method of combating phytopathogenic diseases on crop plants or for seed dressing.
It is known that certain pyrimidin-4-one derivatives have biological activity against phytopathogenic fungi, e.g. known from WO 97/02262 where their properties and methods of preparation are described. On the other hand azole fungicides, phthalimides, phenylamides, morpholines and aminopyrimidines are widely known as plant fungicides for application in various crops of cultivated plants. However, crop tolerance and activity against phytopathogenic plant fungi do not always satisfy the needs of agricultural practice in many incidents and aspects.
It has now been found that the use of
a) a pyrimidin-4-one of formula I 
xe2x80x83wherein
R1 is hydrogen or halogen,
R2 is hydrogen or halogen, and at least one of R1 and R2 is different from hydrogen;
R22 is C1-C5alkyl or xe2x80x94CH2-cyclopropyl and
R23 is C1-C5alkyl or xe2x80x94CH2-cyclopropyl;
in association with
b) either an anilinopyrimidine of formula II 
xe2x80x83wherein
R3 is methyl, 1-propynyl or cyclopropyl;
or an azole of formula III 
xe2x80x83wherein
A is selected from 
whereby the xcex2-carbon attaches to benzene ring of formula III, and wherein R4 is H, F, Cl, phenyl, 4-fluorophenoxy or 4-chlorophenoxy;
R5 is H, Cl or F;
R6 and R7 are independently H or CH3;
R8 is C1-4alkyl or cyclopropyl;
R9 is 4-chlorophenyl or 4-fluorophenyl; and
R11 is allyloxy, C1-4alkyl, or 1,1,2,2-tetrafluoroethoxy-methyl, and the salts of such azole fungicide;
or a morpholine fungicide of formula IV 
xe2x80x83wherein
R12 is C8-15cycloalkyl, and the salts of such morpholine fungicide;
or a strobilurin compound of formula V 
xe2x80x83wherein
X is O,
Y is N, and
R13 is 4-(3-trifluoromethylphenyl)-3-aza-2-oxa-3-pentenyl;
or a pyrrole compound of the formula VI 
xe2x80x83wherein
R14 and R15 are independently halo, or together from a perhalomethylendioxo bridge;
or a phenylamide of the formula VII 
xe2x80x83wherein
R16 is benzyl, methoxymethyl, 2-furanyl, chloromethyl or 
R17 is 1-methoxycarbonyl-ethyl, or 
Z is CH or N,
R20 is hydrogen or methyl,
R21 is hydrogen or methyl;
or a dithiocarbamate fungicide selected from mancozeb, maneb, metiram and zineb;
or a copper compound selected from copper hydroxide, copper oxychloride, copper sulfate and oxine-copper;
or sulfur;
or a phthalimide compound of the formula VIII 
xe2x80x83wherein
R18 and R19 together form a 4-membered bridge xe2x80x94CH2xe2x80x94CHxe2x95x90CHxe2x80x94CH2xe2x80x94 or xe2x95x90CHxe2x80x94CHxe2x95x90CHxe2x80x94CHxe2x95x90;
or with compound of formula IX 
or with a compound of formula X 
or with a compound of formula XI 
or with a compound of formula XII 
or with a compound of formula XIII 
or with a compound of formula XIV 
or with a compound of formula XV 
or with a compound of formula XVI 
or with a compound of formula XVII 
or with a compound of formula XIX 
or with a compound of formula XX 
or with a compound of formula XXI 
or with a compound of formula XXIII 
or with a compound of formula XXIV 
or with a compound of formula XXV 
or with a compound of formula XXVI 
or with a compound of formula XXVII 
or with a compound of formula XXVIII 
xe2x80x83wherein
n is 0 or 1 or 2 etc, and
R is hydrogen or xe2x80x94C(xe2x95x90NH)NH2;
is particularly effective in combating or preventing fungal diseases of crop plants. These combinations exhibit synergistic fungicidal activity.
The combinations according to the invention may also comprise more than one of the active components b), if broadening of the spectrum of disease control is desired. For instance, it may be advantageous in the agricultural practice to combine two or three components b) with the any of the compounds of formula I, or with any preferred member of the group of compounds of formula I.
From WO 97/02262 the following specific species of formula I are known:
A preferred embodiment of the present invention is represented by those combination which comprise as component a) a compound of the formula I wherein R1 is chloro or bromo, R2 is chloro or bromo, R22 is n-propyl, n-butyl, i-butyl and R23 is n-propyl, n-butyl, i-butyl.
Among the mixtures of present invention most preference is given to the mixture of compounds 6-chloro-3-n-propyl-2-n-propyloxy-4-(3H)-quinazolinone (compound I.1), 6-bromo-3-n-propyl-2-n-proplyoxy-4-(3H)-quinazolinone (compound I.2), 7-chloro-3-n-propyl-2-n-proplyoxy-4-(3H)-quinazolinone (compound I.3), 7-bromo-3-n-propyl-2-n-proplyoxy-4-(3H)-quinazolinone (compound I.4), 6-chloro-3-n-butyl-2-n-proplyoxy-4-(3H)-quinazolinone (compound I.5), 6-bromo-3-n-butyl-2-n-proplyoxy-4-(3H)-quinazolinone (compound I.6), 7-chloro-3-n-butyl-2-n-propyloxy-4-(3H)-quinazolinone (compound I.7), 7-bromo-3-n-butyl-2-n-proplyoxy-4-(3H)-quinazolinone (compound I.8), 6-chloro-3-i-butyl-2-n-proplyoxy-4-(3H)-quinazolinone (compound I.9) and 6-bromo-3-i-butyl-2-n-proplyoxy-4-(3H)-quinazolinone (compound I.10) with the compounds of component b), especially the commercially available products falling within the given ranges, i.e. the commercial products mentioned throughout this document.
Salts of the azole, amine and morpholine active ingredients are prepared by reaction with acids, e.g., hydrohalo acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid and hydroiodic acid, or sulfuric acid, phosphoric acid or nitric acid, or organic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, glycolic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, formic acid, benzensulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, salicylic acid, p-aminosalicylic acid and 1,2-naphtalenedisulfonic acid.
The active ingredient combinations are effective against phytopathogenic fungi belonging to the following classes: Ascomycetes (e.g. Venturia, Podosphaera, Erysiphe, Monilinia, Sclerotinia, Mycosphaerella, Uncinula); Basidiomycetes (e.g. the genus Hemileia, Rhizoctonia, Tilletia, Puccinia); Fungi imperfecti (e.g. Botrytis, Helminthosporium, Rhynchosporium, Fusarium, Septoria, Cercospora, Alternaria, Pyricularia and Pseudocercosporella herpotrichoides); Oomycetes (e.g. Phytophthora, Peronospora, Bremia, Pythium, Plasmopara).
Target crops for the areas of indication disclosed herein comprise within the scope of this invention e.g. the following species of plants: cereals (wheat, barley, rye, oats, rice, sorghum and related crops); beet (sugar beet and fodder beet); pomes, stone fruit and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and black-berries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucumber plants (marrows, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocados, cinnamon, camphor); or plants such as maize, tobacco, nuts, coffee, sugar cane, tea, vines, hops, turf, bananas and natural rubber plants, as well as ornamentals (flowers, shrubs, broad-leaved trees and evergreens, such as conifers) and their seeds. This list does not represent any limitation.
The combinations of the present invention may also be used in the area of protecting technical material against attack of fungi. Technical areas include wood, paper, leather, constructions, cooling and heating systems, ventilation and air conditioning systems, and the like. The combinations according the present invention can prevent the disadvantageous effects such as decay, discoloration or mold.
The combinations according to the present invention are particularly effective against powdery mildews and rusts, pyrenophora, rhynchosporium and leptosphaeria fungi, in particular against pathogens of monocotyledonous plants such as cereals, including wheat and barley. They are furthermore particularly effective against downy mildew species, especially against plasmopara in vine.
The amount of combination of the invention to be applied, will depend on various factors such as the compound employed, the subject of the treatment (plant, soil, seed), the type of treatment (e.g. spraying, dusting, seed dressing), the purpose of the treatment (prophylactic or therapeutic), the type of fungi to be treated and the application time.
Particularly preferred mixing partners of the compounds of formula II are those in which R3 is methyl or cyclopropyl. These compounds are commonly known as pyrimethanil and cyprodinil.
Particularly preferred mixing partners of the compounds of formula III are those in which R4 and R5 are Cl, R6 and R7 are H, R8 is ethyl and A is the moiety (ii) (commonly known as etaconazole); those in which R4 and R5 are Cl, R11 is allyloxy and A is the moiety (ix) (commonly known as imazalil); those wherein R4 is chloro, R5, R6 and R7 are H, R8 is n-butyl and A is the moiety (xiv) (commonly known as myclobutanil); and those wherein R4 is phenyl, R6, R7 and R8 are methyl and A is the moiety (xv) (commonly known as bitertanol).
Particularly preferred mixing partners of the compounds of formula IV are those wherein R12 is cyclododecyl (commonly known as dodemorph). Predominantly, the cis-positioning of the methyl groups at the morpholine ring is present in the compounds of formula IV when used in the combinations of the invention.
Particularly preferred mixing partners of the compounds of formula V are those wherein X is O, Y is N and R13 is 4-(3-trifluoromethylphenyl)-3-aza-2-oxa-3-pentenyl.
Particularly preferred mixing partners of the compounds of formula VI are those wherein R14 and R15 are both chloro (commonly known as fenpiclonil); or wherein R14 and R15 together form a bridge xe2x80x94Oxe2x80x94CF2xe2x80x94Oxe2x80x94 (commonly known as fludioxonil).
Particularly preferred mixing partners of the compounds of formula VII are those wherein R16 is benzyl, R20 and R21 are methyl and R17 is 1-methoxycarbonyl-ethyl (commonly known as benalaxyl); or wherein R16 is 2-furanyl, R20 and R21 are methyl and R17 is 1-methoxycarbonyl-ethyl (commonly known as furalaxyl); or wherein R16 is methoxymethyl, R20 and R21 are methyl and R17 is 1-methoxycarbonyl-ethyl or is (R)-1-methoxycarbonyl-ethyl (commonly known as metalaxyl and R-metalaxyl); or wherein R16 is chloromethyl, R20 and R21 are methyl and R17 is 
whereby Z is CH (commonly known as orfurace); or wherein R16 is methoxymethyl, R20 and R21 are methyl and R17 is 
whereby Z is N (commonly known as oxadixyl); or wherein R16 is 
and R17, R20 and R21 is hydrogen (commonly known as carboxin).
Particularly preferred mixing partners of the compounds of formula VIII are those wherein R18 and R19 together form the bridge xe2x80x94CH2xe2x80x94CHxe2x95x90CHxe2x80x94CH2xe2x80x94 (commonly known as captan); or wherein R18 and R19 together form the bridge xe2x95x90CHxe2x80x94CHxe2x95x90CHxe2x80x94CHxe2x95x90 (commonly known as folpet).
The compound of formula IX is commonly known as prochloraz.
The compound of formula X is commonly known as triflumizole.
The compound of formula XI is commonly known as pyrifenox.
The compound of formula XII is commonly known as acibenzolar-S-methyl.
The compound of formula XIII is commonly known as chlorothalonil.
The compound of formula XIV is commonly known as cymoxanil.
The compound of formula XV is commonly known as dimethomorph.
The compound of formula XVI is commonly known as famoxadone.
The compound of formula XVII is commonly known as fenhexamide.
The compound of formula XIX is commonly known as fluazinam.
The compound of formula XX is commonly known as fosetyl-aluminium.
The compound of formula XXI is commonly known as quinoxyfen.
The compound of formula XXIII is commonly known as spiroxamine.
The compound of formula XXIV is commonly known as carbendazime.
The compound of formula XXV is commonly known as thiabendazole.
The compound of formula XXVI is commonly known as ethirimol.
The compound of formula XXVII is commonly known as triazoxide.
The compound of formula XXVIII is commonly known as guazatine.
The specific compounds b) mentioned in the preceding paragraphs are commercially available. Other compounds falling under the scope of the various groups of component b) are obtainable according to procedures analogous to those known for preparing the commercially available compounds.
It has been found that the use of compounds of formulae II to XXVIII in combination with the compound of formula I surprisingly and substantially enhance the effectiveness of the latter against fungi, and vice versa. Additionally, the method of the invention is effective against a wider spectrum of such fungi that can be combated with the active ingredients of this method, when used solely.
Specific preferred mixtures according to the present invention are understood to be represented by the combinations of active ingredients of formula I, or any of the subgroups of formula I, or specifically mentioned members of the subgroups with a second fungicide selected from the group comprising pyrimethanil, cyprodinil, etaconazole, imazalil, myclobutanil, bitertanol, dodemorph, mancozeb, maneb, metiram, zineb, copper hydroxide, copper oxychloride, copper sulfate, oxine-copper, sulfur, methyl 2-{2-[4-(3-trifluoromethylphenyl)-3-aza-2-oxa-3-pentenyl]-phenyl}-2-methoxyimino-acetate, fenpicionil, fludioxonil, benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, orfurace, oxadixyl, carboxin, captan, folpet, prochloraz, triflumizole, pyrifenox, acibenzolar-S-methyl, chlorothalonil, cymoxanil, dimethomorph, famoxadone, fenhexamide, fluazinam, fosetyl-aluminium, quinoxyfen, spiroxamine, carbendazime, thiabendazol, ethirimol, triazoxide and guazatine.
From this group a subgroup b1 is preferred comprising combinations with prochloraz.
A further preferred subgroup b2 comprises combinations with comprising cyprodinil, methyl 2-{2-[4-(3-trifluoromethylphenyl)-3-aza-2-oxa-3-pentenyl]-phenyl}-2-methoxyimino-acetate, acibenzolar-S-methyl, chlorothalonil, famoxadone, quinoxyfen and carbendazime.
From this group combinations with cyprodinil, methyl 2-{2-[4-(3-trifluoromethylphenyl)-3-aza-2-oxa-3-pentenyl]-phenyl}-2-methoxyimino-acetate and acibenzolar-S-methyl are of particular interest as preferred embodiments of this invention as subgroup b2a.
Further combinations of interest are the following:
compound I.1 with any member of groups b1 and b2, or with any member of group b2a;
compound I.2 with any member of groups b1 and b2, or with any member of group b2a;
compound I.3 with any member of groups b1 and b2, or with any member of group b2a;
compound I.4 with any member of groups b1 and b2, or with any member of group b2a.
compound I.5 with any member of groups b1 and b2, or with any member of group b2a;
compound I.6 with any member of groups b1 and b2, or with any member of group b2a;
compound I.7 with any member of groups b1 and b2, or with any member of groups b2a;
compound I.8 with any member of groups b1 and b2, or with any member of group b2a;
compound I.9 with any member of groups b1 and b2, or with any member of group b2a;
compound I.10 with any member of groups b1 and b2, or with any member of group b2a.
The weight ratio of a):b) is so selected as to give a synergistic fungicidal action. In general the weight ratio of a):b) is between 100:1 and 1:400. The synergistic action of the composition is apparent from the fact that the fungicidal action of the composition of a)+b) is greater than the sum of the fungicidal actions of a) and b).
Where the component b) is an anilinopyrimidine of formula II the weight ratio of a):b) is for example between 1:2 and 1:36, especially 1:2 and 1:18, and more preferably 1:3 and 1:8.
Where the component b) is an azole fungicide of formula III the weight ratio of a):b) is for example between 10:1 and 1:20, especially 5:1 and 1:10, and more preferably 2:1 and 1:4.
Where component b) is a morpholine fungicide of formula IV, the weight ratio of a):b) is for example between 1:2 and 1:30, especially 1:3 and 1:15, and more preferably 1:3 and 1:10.
Where component b) is a strobilurin fungicide of formula V, the weight ratio of a):b) is for example between 2:1 and 1:10, especially 1:1.5 and 1:8, and more preferably 1:2 and 1:5.
Where component b) is a pyrrole fungicide of formula VI, the weight ratio of a):b) is for example between 80:1 and 1:30, especially 10:1 and 1:7, and more preferably 10:1 and 1:5.
Where component b) is a phenylamide fungicide of formula VII, the weight ratio of a):b) is for example between 3:1 and 1:12, especially 2.5:1 and 1:6, and more preferably 2:1 to 1:3.
Where component b) is a dithiocarbamate fungicide, the weight ratio of a):b) is for example between 1:3 and 1:120, especially 1:4 and 1:60, and more preferably 1:7 and 1:25.
Where component b) is a copper compound fungicide, the weight ratio of a):b) is for example between 1:1.5 and 1:100, especially 1:2 and 1:50, and more preferably 1:5 and 1:30.
Where component b) is a sulfur fungicide, the weight ratio of a):b) is for example between 1:6 and 1:400, especially 1:8 and 1:200, and more preferably 1:10 and 1:100.
Where component b) is a phthalimide fungicide of formula VIII, the weight ratio of a):b) is for example between 1:3 and 1:80, especially 1:4 and 1:40, and more preferably 1:8 and 1:20.
Where component b) is the compound of formula IX, the weight ratio of a):b) is for example between 1:2 and 1:25, especially 1:4 and 1:12, and more preferably 1:5 and 1:8.
Where component b) is the compound of formula X, the weight ratio of a):b) is for example between 3:1 and 1:16, especially 2.5:1 and 1:8, and more preferably 1:1 and 1:4.
Where component b) is the compound of formula XI, the weight ratio of a):b) is for example between 8:1 and 1:4, especially 2.5:1 and 1:2, and more preferably 2:1 and 1:1.
Where component b) is the compound of formula XII, the weight ratio of a):b) is for example between 6:1 and 1:2, especially 6:1 and 2:1, and more preferably 5:1 and 2:1.
Where component b) is the compound of formula XIII, the weight ratio of a):b) is for example between 1:3 and 1:40, especially 1:4 and 1:20, and more preferably 1:5 and 1:10.
Where component b) is the compound of formula XIV, the weight ratio of a):b) is for example between 3:1 and 1:8, especially 2.5:1 and 1:4, and more preferably 2:1 and 1:2.
Where component b) is the compound of formula XV, the weight ratio of a):b) is for example between 1.5:1 and 1:12, especially 1:1 and 1:6, and more preferably 1:1 and 1:4.
Where component b) is the compound of formula XVI, the weight ratio of a):b) is for example between 1.5:1 and 1:10, especially 1:1 and 1:5, and more preferably 1:1 and 1:3.
Where component b) is the compound of formula XVII, the weight ratio of a):b) is for example between 2:1 and 1:30, especially 1.5:1 and 1:15, and more preferably 1:1 and 1:5.
Where component b) is the compound of formula XIX, the weight ratio of a):b) is for example between 1.5:1 and 1:12, especially 1:1 and 1:6, and more preferably 1:1 and 1:4.
Where component b) is the compound of formula XX, the weight ratio of a):b) is for example between 1:3 and 1:80, especially 1:4 and 1:40 and more preferably 1:1 and 1:25.
Where component b) is the compound of formula XXI, the weight ratio of a):b) is for example between 2:1 and 1:5, especially 1.5:1 and 1:2.5, and more preferably 1:1 and 1:2.
Where component b) is the compound of formula XXIII, the weight ratio of a):b) is for example between 1:2.5 and 1:30, especially 1:3 and 1:15, and more preferably 1:3 and 1:10.
Where component b) is the compound of formula XXIV, the weight ratio of a):b) is for example between 1.5:1 and 1:10, especially 1:1 and 1:5, and more preferably 1:2 and 1:4.
Where component b) is the compound of formula XXV, the weight ratio of a):b) is for example between 1:2.5 and 1:30, especially 1:3 and 1:15, and more preferably 1:3 and 1:10.
Where component b) is the compound of formula XXVI, the weight ratio of a):b) is for example between 1:2 and 1:30, especially 1:3 and 1:15, and more preferably 1:3 and 1:10.
Where component b) is the compound of formula XXVII, the weight ratio of a):b) is for example between 1:5 and 1:30, especially 1:3 and 1.15, and more preferably 1:3 and 1:10.
Where component b) is the compound of formula XXVIII, the weight ratio of a):b) is for example between 1:2.5 and 1:30, especially 1:3 and 1:15, and more preferably 1:3 and 1:10.
The method of the invention comprises applying to the plants to be treated or the locus thereof in admixture or separately, a fungicidally effective aggregate amount of a compound of formula I and a compound of component b).
The term locus as used herein is intended to embrace the fields on which the treated crop plants are growing, or where the seeds of cultivated plants are sown, or the place where the seed will be placed into the soil. The term seed is intended to embrace plant propagating material such as cuttings, seedlings, seeds, germinated or soaked seeds.
The novel combinations are extremely effective on a broad spectrum of phytopathogenic fungi, in particular from the Ascomycetes and Basidiomycetes classes. Some of them have a systemic action and can be used as foliar and soil fungicides.
The fungicidal combinations are of particular interest for controlling a large number of fungi in various crops or their seeds, especially wheat, rye, barley, oats, rice, maize, lawns, cotton, soybeans, coffee, sugarcane, fruit and ornamentals in horticulture and viticulture, and in vegetables such as cucumbers, beans and cucurbits.
The combinations are applied by treating the fungi or the seeds, plants or materials threatened by fungus attack, or the soil with a fungicidally effective amount of the active ingredients.
The agents may be applied before or after infection of the materials, plants or seeds by the fungi.
The novel combinations are particularly useful for controlling the following plant diseases:
Erysiphe graminis in cereals,
Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits,
Podosphaera leucotricha in apples,
Uncinula necator in vines,
Puccinia species in cereals,
Rhizoctonia species in cotton, rice and lawns,
Ustilago species in cereals and sugarcane,
Venturia inaequalis (scab) in apples,
Helminthosporium species in cereals,
Septoria nodorum in wheat,
Septoria tritici in wheat wheat,
Rhynchosporium secalis on barley,
Pseudocercosporella herpotrichoides in wheat and barley,
Pyrenophera teres in barley,
Phytophthora infestans in potatoes and tomatoes,
Fusarium and Verticillium species in various plants,
Plasmopara viticola in grapes,
Alternaria species in fruit and vegetables.
When applied to the plants the compound of formula I is applied at a rate of 25 to 150 g/ha, particularly 50 to 125 g/ha, e.g. 75, 100, or 125 g/ha, in association with 20 to 3000 g/ha, particularly 20 to 2000 g/ha, e.g. 20 g/ha, 30 g/ha, 40 g/ha, 75 g/ha, 80 g/ha, 100 g/ha, 125 g/ha, 150 g/ha, 175 g/ha, 200 g/ha, 300 g/ha, 500 g/ha, 1000 g/ha, 1200 g/ha, 1500 g/ha, 2000 g/ha, or in some cases like sulfur up to 10000 g/ha of a compound of component b), depending on the class of chemical employed as component b).
Where the component b) is an anilinopyrimidine of formula II for example 300 to 900 g a.i./ha is applied in association with the compound of formula I. Where the component b) is an azole fungicide of formula III for example 20 to 350 g a.i./ha is applied in association with the compound of formula I. Where the component b) is an morpholine of formula IV for example 300 to 750 g a.i./ha is applied in association with the compound of formula I. Where the component b) is a strobilurin of formula V for example 75 to 250 g a.i./ha is applied in association with the compound of formula I. Where the component b) is a pyrrole of formula VI for example 200 to 750 g a.i./ha is applied in association with the compound of formula I. Where the component b) is a phenylamide of formula VII for example 50 to 300 g a.i./ha is applied in association with the compound of formula I. Where the component b) is a dithiocarbamate for example 500 to 3000 g a.i./ha is applied in association with the compound of formula I. Where the component b) is a copper compound for example 250 to 2500 g a.i. is applied in association with the compound of formula I. Where the component b) is sulfur for example 1000 to 10000 g a.i. is applied in association with the compound of formula I. Where the component b) is a phthalimide of formula VIII for example 500 to 2000 g a.i./ha is applied in association with the compound of formula I. Where the component b) is the compound of formula IX for example 400 to 600 g a.i./ha is applied in association with the compound of formula I. Where the component b) is the compound of formula X for example 50 to 400 g a.i./ha is applied in association with the compound of formula I. Where the component b) is the compound of formula XI for example 20 to 100 g a.i./ha is applied in association with the compound of formula I. Where the component b) is the compound of formula XII for example 20 to 40 g a.i./ha is applied in association with the compound of formula I. Where the component b) is the compound of formula XIII for example 500 to 1000 g a.i./ha is applied in association with the compound of formula I. Where the component b) is the compound of formula XIV for example 50 to 200 g a.i./ha is applied in association with the compound of formula I. Where the component b) is the compound of formula XV for example 100 to 300 g a.i./ha is applied in association with the compound of formula I. Where the component b) is the compound of formula XVI for example 125 to 250 g a.i./ha is applied in association with the compound of formula I. Where the component b) is the compound of formula XVII for example 100 to 750 g a.i./ha is applied in association with the compound of formula I. Where the component b) is the compound of formula XIX for example 100 to 300 g a.i./ha is applied in association with the compound of formula I. Where the component b) is the compound of formula XX for example 500 to 2000 g a.i./ha is applied in association with the compound of formula I. Where the component b) is the compound of formula XXI for example 75 to 125 g a.i./ha is applied in association with the compound of formula I. Where the component b) is the compound of formula XXIII for example 375 to 750 g a.i./ha is applied in association with the compound of formula I. Where the component b) is the compound of formula XXIV for example 125 to 250 g a.i./ha is applied in association with the compound of formula I. Where the component b) is the compound of formula XXV for example 5 to 200 g a.i./100 kg is applied for seed dressing in association with the compound of formula I. Where the component b) is the compound of formula XXVI for example 200 g a.i./100 kg is applied for seed dressing in association with the compound of formula I. Where the component b) is the compound of formula XXVII for example 2 g a.i./100 kg is applied for seed dressing in association with the compound of formula I. Where the component b) is the compound of formula XXVIII for example 40 to 80 g a.i./100 kg is applied for seed dressing in association with the compound of formula I.
In agricultural practice the application rates of the combination depend on the type of effect desired, and range from 0.02 to 4 kg of active ingredient per hectare.
When the active ingredients are used for treating seed, rates of 0.001 to 50 g a.i. per kg, and preferably from 0.01 to 10 g per kg of seed are generally sufficient.
The invention also provides fungicidal compositions comprising a compound of formula I and a compound of component b).
The composition of the invention may be employed in any conventional form, for example in the form of a twin pack, an instant granulate, a flowable or a wettable powder in combination with agriculturally acceptable adjuvants. Such compositions may be produced in conventional manner, e.g. by mixing the active ingredients with appropriate adjuvants (diluents or solvents and optionally other formulating ingredients such as surfactants).
The term diluent as used herein means any liquid or solid agriculturally acceptable material including carriers which may be added to the active constituents to bring them in an easier or improved applicable form, respectively, to a usable or desirable strength of activity. Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates, such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons, such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones, such as cyclohexanone, strongly polar solvents, such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, as well as vegetable oils or epoxidised vegetable oils, such as epoxidised coconut oil or soybean oil; or water. The solid carriers used, e.g. for dusts and dispersible powders, are normally natural mineral fillers, such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite, and suitable non-absorbent carriers are, for example, calcite or sand. In addition, a great number of materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverized plant residues. Depending upon the nature of the compounds of formula I and component b) to be formulated, suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. The term xe2x80x9csurfactantsxe2x80x9d will also be understood as comprising mixtures of surfactants. Particularly advantageous application-promoting adjuvants are also natural or synthetic phospholipids of the cephalin and lecithin series, e.g. phosphatidylethanolamine, phosphatidylserine, phosphatidylglycerol and lysolecithin.
Particularly formulations to be applied in spraying forms such as water dispersible concentrates or wettable powders may contain surfactants such as wetting and dispersing agents, e.g. the condensation product of formaldehyde with naphthalene sulphonate, an alkylarylsulphonate, a lignin sulphonate, a fatty alkyl sulphate, and ethoxylated alkylphenol and an ethoxylated fatty alcohol.
A seed dressing formulation is applied in a manner known per se to the seeds employing the combination of the invention and a diluent in suitable seed dressing formulation form, e.g. as an aqueous suspension or in a dry powder form having good adherence to the seeds. Such seed dressing formulations are known in the art. Seed dressing formulations may contain the single active ingredients or the combination of active ingredients in encapsulated form, e.g. as slow release capsules or microcapsules.
In general, the formulations include from 0.01 to 90% by weight of active agent, from 0 to 20% agriculturally acceptable surfactant and 10 to 99.99% solid or liquid adjuvant(s), the active agent consisting of at least the compound of formula I together with a compound of component b), and optionally other active agents, particularly microbes or conservatives or the like.
Concentrate forms of compositions generally contain in between about 2 and 80%, preferably between about 5 and 70% by weight of active agent. Application forms of formulation may for example contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight of active agent.
The Examples which follow serve to illustrate the invention, xe2x80x9cactive ingredientxe2x80x9d denoting a mixture of compound I and a compound of component b) in a specific mixing ratio. Formulations may be prepared analogously to those described in, for example, WO 97/33890.
Slow Release Capsule Suspension
28 parts of a combination of the compound of formula I and a compound of component b), or of each of these compounds separately, are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1). This mixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved. To this emulsion a mixture of 2.8 parts 1,6-diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed.
The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The capsule suspension formulation contains 28% of the active ingredients. The medium capsule diameter is 8-15 microns.
Seed Dressing Formulation
25 parts of a combination of the compound of formula I and a compound of component b), 15 parts of diaikylphenoxypoly(ethylenoxy)ethanol, 15 parts of fine silica, 44 parts of fine kaolin, 0.5 parts of Rhodamine B as a colorant and 0.5 parts of Xantham Gum are mixed and ground in a contraplex mill at approx. 10000 rpm to an average particle size of below 20 microns.
The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.
Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.